CN100500737C - Method of synthesizing polyethylene glycol perfluoroolefin ether - Google Patents
Method of synthesizing polyethylene glycol perfluoroolefin ether Download PDFInfo
- Publication number
- CN100500737C CN100500737C CNB2007100668821A CN200710066882A CN100500737C CN 100500737 C CN100500737 C CN 100500737C CN B2007100668821 A CNB2007100668821 A CN B2007100668821A CN 200710066882 A CN200710066882 A CN 200710066882A CN 100500737 C CN100500737 C CN 100500737C
- Authority
- CN
- China
- Prior art keywords
- polyethylene glycol
- boric acid
- synthetic method
- ether
- perfluoroolefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention discloses a synthesizing method of carbowax full fluorine alkylene methyl ether, which comprises the following steps: putting carbowax and boric acid into polar solvent; esterifying undeThe invention discloses a synthesizing method of carbowax full fluorine alkylene methyl ether, which comprises the following steps: putting carbowax and boric acid into polar solvent; esterifying under 30-80 deg.c till reacting completely; adding into full fluoro-olefin oligomerisation body and organic amine activator; proceeding etherified reaction under 30-80 deg.c; steaming out organic solvent r 30-80 deg.c till reacting completely; adding into full fluoro-olefin oligomerisation body and organic amine activator; proceeding etherified reaction under 30-80 deg.c; steaming out organic solvent after reacting completely; adding into water; proceeding hydrolytic reaction at 50-70 deg.c; steaming out water; getting CnF2n-1O(CH2CH2O)mH; setting n as 6-12 intact number and m as 4-24 intact numbeafter reacting completely; adding into water; proceeding hydrolytic reaction at 50-70 deg.c; steaming out water; getting CnF2n-1O(CH2CH2O)mH; setting n as 6-12 intact number and m as 4-24 intact number; making mass ratio of boric acid : carbowax : full fluoro-olefin oligomerisation body at 1:2.5-3.5:2.5-3.5; making usage of organic amine activator at 0.1-1.2 double of carbowax. r; making mass ratio of boric acid : carbowax : full fluoro-olefin oligomerisation body at 1:2.5-3.5:2.5-3.5; making usage of organic amine activator at 0.1-1.2 double of carbowax.
Description
(1) technical field
The present invention relates to a kind of synthetic method of polyethylene glycol perfluoroolefin ether.
(2) background technology
Fluorocarbon surfactant is a most important kind in the special surface active agent, and its special performance often is summarized as " three height ", " two hate ", i.e. high surface, high heat-resistant stability and high chemical stability; Its fluorine-containing alkyl is hydrophobic but also hate oil [New Chemical Materials, 2004,32 (8): 46] not only.It is the highest class of surfactivity in the present all surface promoting agent, is mainly used in higher extraordinary occasion of technical requirements or general conventional surfactants field that be difficult to be competent at, that effect is relatively poor.Fluorine-containing nonionogenic tenside is one type more important in the fluorochemical surfactant, its polar group usually by some amount contain oxygen-ether linkage or hydroxyl constitutes.Because the unionization in the aqueous solution of fluorine-containing nonionogenic tenside so stability is high, is not vulnerable to pH value, the influence that ionogen and some inorganic salt exist.And the consistency of it and negatively charged ion, positively charged ion and amphoterics is good, thus be widely used in the industrial production (the fluorocarbon surfactant China's work of once giving birth, chemical engineering industry press, calendar year 2001 first version).
French Patent (FR 2 132 122) has reported that the nonionogenic tenside that contains fluorocarbon radicals is grouped into R
f-Z-O-(CRHCH
2O-)
p-Z-R
f, wherein R is H, methyl or ethyl; Rf is the perfluoroalkyl that contains 3～20 carbon atoms, preferably 6～12 carbon atoms; Z is-CO-,-SO
2-,-CH
2CH
2-,-OC
6H
4CH
2-,-C
6H
4CO-,-C
6H
4SO
2-etc.These compounds are of great use in the application of many protective layers.Water-based paint for example, earth complex luminescent component or other protective cover and decorating film are when the very bright last one coat of needs, especially in the situation of the fast dry coating that does not need follow-up polishing.Fluorocarbon surfactant has improved the character of automatic homogenizing, so surface film obtains suitable improvement.But still there is not the preparation method that document relates to polyethylene glycol perfluoroolefin ether at present.
(3) summary of the invention
The preparation method who the purpose of this invention is to provide a kind of polyethylene glycol perfluoroolefin ether.
The technical solution used in the present invention is as follows:
Polyoxyethylene glycol and boric acid are in polar solvent, 30～80 ℃ of esterifications are complete, add perfluoroolefine oligomer and organic amine catalyzer then, carry out etherification reaction under 30～80 ℃, boil off organic solvent after reacting completely, add entry then, 50～70 ℃ of hydrolysis reaction, reaction finishes, and boils off water, promptly gets described polyethylene glycol perfluoroolefin ether C
nF
2n-1O (CH
2CH
2O)
mH, wherein n is 6～12 integer, m is 4～24 integer, described boric acid: polyoxyethylene glycol: the amount of substance of perfluoroolefine oligomer is than being 1:2.5～3.5:2.5～3.5,0.1～1.2 times of the amount of substance that described organic amine catalyst consumption is a polyoxyethylene glycol.Reasonable, the water that described hydrolysis reaction adds is 5～10:1 with the ratio of boric acid amount of substance.
General, above-mentioned reaction time of esterification is 3～10h, and the described etherification reaction time is 1～3h, and the time of described hydrolysis reaction is 5～8h.
In this reaction process, boric acid gets up the hydroxyl protection of polyoxyethylene glycol one end earlier, generates the boric acid macrogol ester; Reaction intermediate adds perfluoroolefine oligomer and catalyzer without separation, directly carries out etherification reaction, and promptly Sheng Xia unreacted polyoxyethylene glycol hydroxyl is reacted into ether with the perfluoroolefine oligomer again; After treating that hydroxyl reaction is fully, be cooled to certain temperature, add an amount of water, the reaction that is hydrolyzed at a certain temperature, hydrolysis reaction steams solvent and water after finishing, and obtains viscous liquid C
nF
2n-1O (CH
2CH
2O)
mH, n=6～12, m is 4～24 integer, is polyethylene glycol perfluoroolefin ether.
Hydrolysising reacting temperature is unsuitable too high, with 50～70 ℃ better, in order to avoid ether bond rupture.
Further, the organic amine catalyzer described in the method is the arbitrary proportion mixture of following one or several: dimethylamine, diethylamine, Trimethylamine 99, triethylamine, N-methyl piperidine, N, N-xylidene(s), pyridine or piperidines;
Further again, described polar solvent is the arbitrary proportion mixture of following one or several: ethylene dichloride, trichloromethane, tetrahydrofuran (THF) or dimethyl sulfoxide (DMSO), the consumption of polar solvent are 1～3 times of polyoxyethylene glycol weight.
It is one of following that described polyoxyethylene glycol is preferably: Liquid Macrogol, poly(oxyethylene glycol) 400, Polyethylene Glycol-600, polyoxyethylene glycol 800 or cetomacrogol 1000.It is one of following that described perfluoroolefine oligomer can be selected: the tetrafluoroethylene tetramer, tetrafluoroethylene pentamer, tetrafluoroethylene six aggressiveness, hexafluoropropylene dimmer or hexafluoropropylene trimer.
In the method, described polyoxyethylene glycol and boric acid reaction conditions preferably are to carry out esterification 4～6h at 50～70 ℃.
Comparatively concrete, the synthetic method of described polyethylene glycol perfluoroolefin ether is carried out according to following steps: polyoxyethylene glycol and boric acid are in polar solvent, 50～70 ℃ of reaction 4～6h, add perfluoroolefine oligomer and organic amine catalyzer then, boil off organic solvent behind 30～80 ℃ of etherification reaction 1～3h, 5 times the water of amount of substance that is incorporated as boric acid then boils off water at 50～70 ℃ of hydrolysis reaction 5～8h, promptly gets described polyethylene glycol perfluoroolefin ether C
nF
2n-1O (CH
2CH
2O)
mH, wherein n is 6～12 integer, m is 4～24 integer, described boric acid: polyoxyethylene glycol: the amount of substance of perfluoroolefine oligomer is than being 1:2.5～3.5:2.5～3.5.
The present invention compared with prior art, its beneficial effect is embodied in:
Present method adopts one kettle way to prepare polyethylene glycol perfluoroolefin ether, and is simple to operation, and synthetic polyethylene glycol perfluoroolefin ether purity height is low with the aqueous solution surface tension of its preparation.
(4) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1
In four-hole boiling flask, add ethylene dichloride 120mL, Polyethylene Glycol-600 49.5g, under agitation, and the limit heating, the limit slowly adds boric acid 1.7g, and temperature is controlled at 80 ℃, reacts 3 hours.Add hexafluoropropylene trimer 37.1g, pyridine 7.8g, 80 ℃ were reacted 1 hour.Steam solvent, add 2.5mL water while hot and be hydrolyzed.Hydrolysis temperature is controlled at 70 ℃, reacts 8 hours.Carry out underpressure distillation after the cooling again, steam excessive water, obtain C
9F
17O (CH
2CH
2O)
13H glues shape liquid, and its 0.1% aqueous solution surface tension is 24.2mN/m.
Embodiment 2
In four-hole boiling flask, add tetrahydrofuran (THF) 50mL, Liquid Macrogol 20.6g, under agitation, and the limit heating, the limit slowly adds boric acid 1.7g, and temperature is controlled at 30 ℃, reacts 10 hours.Add hexafluoropropylene dimmer 20.6g, N, accelerine 0.83g, 60 ℃ were reacted 3 hours.Steam solvents tetrahydrofurane.Adding 5mL water while hot is hydrolyzed.Hydrolysis temperature is controlled at 70 ℃, reacts 5 hours.Distill again after the cooling, steam excessive water, obtain C
6F
11O (CH
2CH
2O)
6H glues shape liquid, and its 0.1% aqueous solution surface tension is 26.7mN/m.
Embodiment 3
In four-hole boiling flask, add trichloromethane 35mL, cetomacrogol 1000 50g, under agitation, and the limit heating, the limit slowly adds boric acid 1.7g, and temperature is controlled at 50 ℃, reacts 3 hours.Add tetrafluoroethylene tetramer 38.5g, triethylamine 7.8g, 30 ℃ were reacted 3 hours.Steam the solvent trichloromethane.Adding 4mL water while hot is hydrolyzed.Hydrolysis temperature is controlled at 50 ℃, reacts 8 hours.Carry out underpressure distillation after the cooling again, steam excessive water, obtain C
8F
15O (CH
2CH
2O)
22The orange-yellow sticking shape liquid of H, its 0.1% aqueous solution surface tension is 25.6mN/m.
Embodiment 4
In four-hole boiling flask, add dimethyl sulfoxide (DMSO) 60mL, polyoxyethylene glycol 800 66g, under agitation, and the limit heating, the limit slowly adds boric acid 1.5g, and temperature is controlled at 70 ℃, reacts 4 hours.Add tetrafluoroethylene six aggressiveness 49.5g, piperidines 7g, 70 ℃ were reacted 2 hours.Decompression steams the solvent dimethyl sulfoxide (DMSO).Adding 5mL water while hot is hydrolyzed.Hydrolysis temperature is controlled at 70 ℃, reacts 6 hours.Carry out underpressure distillation after the cooling again, steam excessive water, obtain C
12F
23O (CH
2CH
2O)
18The orange-yellow sticking shape liquid of H, its 0.1% aqueous solution surface tension is 24.9mN/m.
Claims (10)
1. the synthetic method of a polyethylene glycol perfluoroolefin ether, it is characterized in that described method is that polyoxyethylene glycol and boric acid are in polar solvent, 30～80 ℃ of esterifications add perfluoroolefine oligomer and organic amine catalyzer then to reacting completely, and carry out etherification reaction under 30～80 ℃, boil off organic solvent after reacting completely, add entry then, 50～70 ℃ of hydrolysis reaction, reaction finishes, boil off water, promptly get described polyethylene glycol perfluoroolefin ether C
nF
2n-1O (CH
2CH
2O)
mH, wherein n is 6～12 integer, m is 4～24 integer, described boric acid: polyoxyethylene glycol: the amount of substance of perfluoroolefine oligomer is than being 1:2.5～3.5:2.5～3.5,0.1～1.2 times of the amount of substance that described organic amine catalyst consumption is a polyoxyethylene glycol.
2. the synthetic method of polyethylene glycol perfluoroolefin ether as claimed in claim 1 is characterized in that described reaction time of esterification is 3～10h, and the described etherification reaction time is 1～3h, and the time of described hydrolysis reaction is 5～8h.
3. the synthetic method of polyethylene glycol perfluoroolefin ether as claimed in claim 1, it is characterized in that described organic amine catalyzer is the arbitrary proportion mixture of following one or several: dimethylamine, diethylamine, Trimethylamine 99, triethylamine, N-methyl piperidine, N, N-xylidene(s), pyridine or piperidines.
4. the synthetic method of polyethylene glycol perfluoroolefin ether as claimed in claim 1 is characterized in that described polar solvent is the arbitrary proportion mixture of following one or several: ethylene dichloride, trichloromethane, tetrahydrofuran (THF) or dimethyl sulfoxide (DMSO).
5. the synthetic method of polyethylene glycol perfluoroolefin ether as claimed in claim 4, the consumption that it is characterized in that described polar solvent is 1～3 times of polyoxyethylene glycol weight.
6. the synthetic method of polyethylene glycol perfluoroolefin ether as claimed in claim 1 is characterized in that the water that described hydrolysis reaction adds is 5～10:1 with boric acid amount of substance ratio.
7. the synthetic method of polyethylene glycol perfluoroolefin ether as claimed in claim 1 is characterized in that described polyoxyethylene glycol is one of following: Liquid Macrogol, poly(oxyethylene glycol) 400, Polyethylene Glycol-600, polyoxyethylene glycol 800 or cetomacrogol 1000.
8. the synthetic method of polyethylene glycol perfluoroolefin ether as claimed in claim 1 is characterized in that described perfluoroolefine oligomer is the tetrafluoroethylene tetramer, tetrafluoroethylene pentamer, tetrafluoroethylene six aggressiveness, hexafluoropropylene dimmer or hexafluoropropylene trimer.
9. the synthetic method of polyethylene glycol perfluoroolefin ether as claimed in claim 1 is characterized in that described polyoxyethylene glycol and boric acid carry out esterification 4～6h at 50～70 ℃.
10. as the synthetic method of the described polyethylene glycol perfluoroolefin ether of one of claim 1～9, it is characterized in that described method carries out according to following steps: polyoxyethylene glycol and boric acid are in polar solvent, 50～70 ℃ of reaction 4～6h, add perfluoroolefine oligomer and organic amine catalyzer then, boil off organic solvent behind 30～80 ℃ of etherification reaction 1～3h, 5 times the water of amount of substance that is incorporated as boric acid then is at 50～70 ℃ of hydrolysis reaction 5～8h, boil off water, promptly get described polyethylene glycol perfluoroolefin ether C
nF
2n-1O (CH
2CH
2O)
mH, wherein n is 6～12 integer, m is 4～24 integer, described boric acid: polyoxyethylene glycol: the amount of substance of perfluoroolefine oligomer is than being 1:2.5～3.5:2.5～3.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100668821A CN100500737C (en) | 2007-01-23 | 2007-01-23 | Method of synthesizing polyethylene glycol perfluoroolefin ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100668821A CN100500737C (en) | 2007-01-23 | 2007-01-23 | Method of synthesizing polyethylene glycol perfluoroolefin ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101016377A CN101016377A (en) | 2007-08-15 |
| CN100500737C true CN100500737C (en) | 2009-06-17 |
Family
ID=38725612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100668821A Expired - Fee Related CN100500737C (en) | 2007-01-23 | 2007-01-23 | Method of synthesizing polyethylene glycol perfluoroolefin ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100500737C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102210995B (en) * | 2011-04-06 | 2014-01-29 | 浙江工业大学 | Polyglycerol perfluoroalkenyl ether mixture and preparation method thereof |
| CN104974019B (en) * | 2015-06-11 | 2016-08-24 | 浙江工业大学 | A kind of allyl ether series fluorochemical monomer and synthetic method thereof and application |
| TW201943762A (en) * | 2018-04-20 | 2019-11-16 | 義大利商首威專業聚合物義大利公司 | Process for the manufacture of polyether polymers |
| CN111621279A (en) * | 2020-06-05 | 2020-09-04 | 赛科思能源技术(重庆)有限责任公司 | Imbibition oil displacement agent for improving recovery ratio in middle and later periods of oilfield development |
| CN114890874A (en) * | 2022-04-02 | 2022-08-12 | 浙江大学衢州研究院 | Fluorine-containing surfactant and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4079084A (en) * | 1972-03-15 | 1978-03-14 | Imperial Chemical Industries Limited | Fluorocarbon surfactants |
| US4408043A (en) * | 1982-03-08 | 1983-10-04 | Nalco Chemical Company | Fluorocarbon surfactants |
-
2007
- 2007-01-23 CN CNB2007100668821A patent/CN100500737C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4079084A (en) * | 1972-03-15 | 1978-03-14 | Imperial Chemical Industries Limited | Fluorocarbon surfactants |
| US4408043A (en) * | 1982-03-08 | 1983-10-04 | Nalco Chemical Company | Fluorocarbon surfactants |
Non-Patent Citations (2)
| Title |
|---|
| 支链型醚类全氟表面活性剂的合成与表面活性. 吴蕾，徐春柳等.化工生产与技术，第13卷第6期. 2006 * |
| 氟两相体系及其在有机合成中的应用. 史鸿鑫.云南化工，第32卷第5期. 2005 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101016377A (en) | 2007-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI579427B (en) | Fabric softener active composition | |
| CN100500737C (en) | Method of synthesizing polyethylene glycol perfluoroolefin ether | |
| CN101016376B (en) | Method of synthesizing polyethylene glycol perfluoroolefin methyl ether | |
| CN104645877B (en) | Bola type polyether modified organic silicon surfactant and preparation method thereof | |
| CN108586687B (en) | Preparation method of two-block nonionic polyurethane fluorine-containing short-chain surfactant | |
| CN106349463A (en) | Odorless alkyd resin and preparation method thereof | |
| CN102974268A (en) | Alkylbenzyl polyoxyethylene ether betaine surfactant and its preparation method and use | |
| CN106029630B (en) | Fluorosurfactants | |
| CN105017097B (en) | Surfactant N carboxyethyls, the preparation method of 3 dimethylamino-propyl perfluoro hexyl sulfonamide of N | |
| CN111499550B (en) | Fluorine-containing surfactant and preparation method and application thereof | |
| CN103508892A (en) | Synthetic method for phthalate compound | |
| CN105521743A (en) | Cationic surfactant and synthetic method thereof | |
| CN102500087A (en) | Method for preparing perfluorohexane surfactant serving as main agent of aqueous film-forming extinguishing agent directly | |
| CN101475498B (en) | Preparation method of 3-dehydroabietylamine-2-hydroxypropyl trimethyl ammonium chloride | |
| CN110354755A (en) | A kind of novel fluorine betaine type amphoteric surfactant and its preparation method and application | |
| CN103585926B (en) | Acid-base resistant polyether modified trisiloxane surfactant as well as preparation and application thereof | |
| CN103374029A (en) | Preparation method of fatty alcohol polyoxyethylene phosphate ester potassium salt | |
| CN102351721A (en) | Double-long chain ester-based quaternary ammonium salt and synthesis technology thereof | |
| CN101433813B (en) | Hexafluoropropylene-based quaternary ammonium salt cationic surfactant, synthesizing method and use | |
| CN102671576A (en) | Quaternary ammonium cationic surfactant and synthetic method thereof | |
| CN102766065B (en) | Synthetic method of fluorocarbon surfactant N-2 hydroxyethyl perfluorocarbon symplectic amide | |
| JP2010241860A (en) | Liquid detergent composition | |
| CN105130835A (en) | Palmitoleic acid monoisopropanolamide synthesis method | |
| CN101703906B (en) | Cationic gemini surfactant containing tri-ester groups and preparation method thereof | |
| CN103524344A (en) | Preparation method of ethoxylation (2) 1, 6-hexanediol diacrylate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090617 Termination date: 20120123 |